EP0806436A1 - Procédé de préparation de copolymères EP(D)M élastomériques - Google Patents

Procédé de préparation de copolymères EP(D)M élastomériques Download PDF

Info

Publication number
EP0806436A1
EP0806436A1 EP97201335A EP97201335A EP0806436A1 EP 0806436 A1 EP0806436 A1 EP 0806436A1 EP 97201335 A EP97201335 A EP 97201335A EP 97201335 A EP97201335 A EP 97201335A EP 0806436 A1 EP0806436 A1 EP 0806436A1
Authority
EP
European Patent Office
Prior art keywords
xylene
bis
general formula
propylene
zirconium dichloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97201335A
Other languages
German (de)
English (en)
Other versions
EP0806436B1 (fr
Inventor
Viviano Banzi
Liliana Gila
Roberto Santi
Paolo Biagini
Giampietro Borsotti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enichem SpA
Original Assignee
Enichem SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enichem SpA filed Critical Enichem SpA
Publication of EP0806436A1 publication Critical patent/EP0806436A1/fr
Application granted granted Critical
Publication of EP0806436B1 publication Critical patent/EP0806436B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-propylene copolymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-propylene-diene terpolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/09—Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • o-Xylene- ⁇ , ⁇ '-bis-[ ⁇ 5 -(3-methyl)-inden-1-yl] zirconium dichloride, i.e., metallocene A is prepared by operating as disclosed in Example N. 5 of Italian Patent Application IT-A-MI 95/A 001444,.
  • the data relating to the comparison examples 16a-b reported in table 3 set forth how a catalytic system obtained by starting from a metallocene of general formula (I) in which all R 2 radicals are H and with the A radical having the general formula (Ia) in which R 1 radicals in 3-, 4- and 7- positions are -CH 3 , with the residual R 1 's being all -H, is not capable to produce elastomeric polymers having a high enough Mooney viscosity.
  • This example shows how the catalytic system obtained by starting from a metallocene of general formula (I) in which all R 2 's are H and with the A radical of structure (Ia) having R 1 in 3-position equal to ethyl and all other R 1 's equal to H, is capable of producing high Mooney viscosity elastomeric copolymers in high yield.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP97201335A 1996-05-09 1997-05-03 Procédé de préparation de copolymères EP(D)M élastomériques Expired - Lifetime EP0806436B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI960926 1996-05-09
IT96MI000926A IT1283630B1 (it) 1996-05-09 1996-05-09 Procedimento per la preparazione di copolimeri elastomerici ep(d)m

Publications (2)

Publication Number Publication Date
EP0806436A1 true EP0806436A1 (fr) 1997-11-12
EP0806436B1 EP0806436B1 (fr) 2000-07-19

Family

ID=11374226

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97201335A Expired - Lifetime EP0806436B1 (fr) 1996-05-09 1997-05-03 Procédé de préparation de copolymères EP(D)M élastomériques

Country Status (12)

Country Link
US (1) US6124413A (fr)
EP (1) EP0806436B1 (fr)
JP (1) JP3986613B2 (fr)
KR (1) KR100257458B1 (fr)
CN (1) CN1098869C (fr)
BR (1) BR9703091A (fr)
CA (1) CA2204177C (fr)
DE (1) DE69702569T2 (fr)
ES (1) ES2148895T3 (fr)
IT (1) IT1283630B1 (fr)
MX (1) MX9703331A (fr)
RU (1) RU2179561C2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092609A1 (fr) * 2001-05-17 2002-11-21 Polimeri Europa S.P.A. Procede pour preparer des copolymeres et des terpolymeres elastomeres d'ep(d)m
WO2003008465A3 (fr) * 2001-07-19 2003-08-28 Univation Tech Llc Composes catalyseurs a metallocene a faible incorporation de comonomere
WO2004052951A1 (fr) * 2002-12-05 2004-06-24 Exxonmobil Chemical Patents Inc. Copolymeres de propylene a modification dienique
EP1464657A1 (fr) * 2003-03-06 2004-10-06 ATOFINA Research Catalyseur du type métallocène hydrogené
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7326756B2 (en) 2002-12-05 2008-02-05 Exxonmobil Chemical Patents Inc. High temperature bulk polymerization of branched crystalline polypropylene
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7994237B2 (en) 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
WO2012048067A3 (fr) * 2010-10-07 2012-11-22 Chevron Phillips Chemical Company Lp Systèmes de catalyseur métallocène ponté avec effets commutables de l'hydrogène et de comonomère

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1298616B1 (it) 1998-03-10 2000-01-12 Enichem Spa Complesso metallocenico pontato per la (co) polimerizzazione delle olefine
KR100342541B1 (ko) * 1998-04-16 2002-06-28 나까니시 히로유끼 올레핀 중합촉매 및 중합방법
US6433203B1 (en) * 1998-11-20 2002-08-13 Basell Technology Company Bv Bridged metallocenes, preparation, use in catalytic systems
US8008412B2 (en) 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
US7439312B2 (en) 2002-10-24 2008-10-21 Exxonmobil Chemical Patents Inc. Branched crystalline polypropylene
KR100586922B1 (ko) 2004-11-18 2006-06-08 금호폴리켐 주식회사 고수율의 이피(디)엠의 제조방법 및 수율의 제어방법,이피(디)엠의 회수방법
US8242237B2 (en) 2006-12-20 2012-08-14 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
ES2446294T3 (es) 2007-06-04 2014-03-07 Exxonmobil Chemical Patents Inc. Polimerización de propileno en un sistema homogéneo en condiciones de superdisolución
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
WO2009082468A1 (fr) 2007-12-20 2009-07-02 Exxonmobil Research And Engineering Company Mélanges de copolymères de polypropylène éthylène-propylène et procédé en ligne pour leur production
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US8318875B2 (en) 2008-01-18 2012-11-27 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization and polypropylenes made therefrom
KR101367402B1 (ko) * 2009-11-27 2014-02-25 주식회사 엘지화학 높은 디엔계 단량체 함량과 고분자량을 가지는 탄성 중합체의 제조방법
US8629292B2 (en) 2010-10-07 2014-01-14 Chevron Phillips Chemical Company Lp Stereoselective synthesis of bridged metallocene complexes
US8609793B2 (en) 2010-10-07 2013-12-17 Chevron Phillips Chemical Company Lp Catalyst systems containing a bridged metallocene
US10800865B2 (en) 2015-09-14 2020-10-13 Exxonmobil Chemical Patents Inc. Process for making branched EPDM and the EPDM therefrom
US20190248934A1 (en) 2018-02-09 2019-08-15 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene Elastomers and Methods of Making Them
EP3802644B1 (fr) 2018-06-04 2024-09-04 ExxonMobil Chemical Patents Inc. Métallocènes comprenant des ponts si-si
CN112218900B (zh) 2018-06-04 2023-07-04 埃克森美孚化学专利公司 包括两种二茂铪催化剂化合物的催化剂体系
US11198747B2 (en) 2018-06-04 2021-12-14 Exxonmobil Chemical Patents Inc. Catalyst systems including two hafnocene catalyst compounds
JP7743720B2 (ja) * 2020-07-01 2025-09-25 日本ポリエチレン株式会社 オレフィン重合用触媒成分、オレフィン重合用触媒、及び、オレフィン重合体の製造方法
KR102603860B1 (ko) * 2022-08-09 2023-11-22 윤정식 패각분말을 고함량 포함하는 조성물 및 이를 이용한 마스터 배치

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347129A1 (fr) * 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Procédé de production d'élastomères EPDM à haut poids moléculaire en utilisant un système catalytique métallocène-alumoxane

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2545006B2 (ja) * 1990-07-03 1996-10-16 ザ ダウ ケミカル カンパニー 付加重合触媒
US5292845A (en) * 1992-01-23 1994-03-08 Mitsui Petrochemical Industries, Ltd. Ethylene/alpha-olefin/7-methyl-1,6-octadiene copolymer rubber and composition of the same
FI945873L (fi) * 1992-06-18 1994-12-14 Spherilene Srl Menetelmä etyleenisen polymeerin valmistamiseksi
EP0629631B1 (fr) * 1993-06-07 2002-08-28 Mitsui Chemicals, Inc. Nouvelle composé métallique de transition, et catalyseur de polymérisation le contenant
EP0812854B2 (fr) * 1993-06-07 2011-04-20 Mitsui Chemicals, Inc. Composé de métal de transition, catalyseur de polymérisation d'oléfines comprenant celui-ci, procédé de polymérisation d'oléfines à l'aide de ce catalyseur et homo- et co-polymère de propylène
IT1271406B (it) * 1993-09-13 1997-05-28 Spherilene Srl Procedimento per la preparazione di polimeri dell'etilene e prodotti ottenuti
IT1270253B (it) * 1994-06-20 1997-04-29 Spherilene Srl Copolimeri dell'etilene e procedimento per la preparazione di polimeri dell'etilene
TW383313B (en) * 1994-12-20 2000-03-01 Mitsui Petrochemical Ind Preparation of ethylene-alpha-olefin-nonconjugate polyene random copolymers, the copolymers obtaining which, and the use of the copolymers
TW383314B (en) * 1994-12-20 2000-03-01 Mitsui Petrochemical Ind Ethylene-alpha-olefin-nonconjugated polyene random copolymer, rubber composition, and process for preparing the random copolymer
US5696213A (en) * 1995-04-21 1997-12-09 Exxon Chemical Patents Inc. Ethylene-α-olefin-diolefin elastomers solution polymerization process
TW326450B (en) * 1995-06-28 1998-02-11 Mitsui Petroleum Chemicals Ind Ethylene copolymer rubber, vulcanizable rubber composition containing the copolymer rubber, and process for preparing the same
IT1275777B1 (it) * 1995-07-06 1997-10-17 Enichem Spa Catalizzatore metallocenico per la (co)polimerizzazione delle olefine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347129A1 (fr) * 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Procédé de production d'élastomères EPDM à haut poids moléculaire en utilisant un système catalytique métallocène-alumoxane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAN T K ET AL: "ETHYLENE AND PROPYLENE POLYMERIZATION OVER CHIRAL ANSA-DICHLORO O-PHENYLENEDIMETHYLENEBIS(N5-1-INDENYL)ZIRCONIUM ZR C6H4(CH2-1-C9H6)2-1,2CL2", MACROMOLECULES, vol. 28, no. 14, 3 July 1995 (1995-07-03), pages 4801 - 4805, XP002030447 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092609A1 (fr) * 2001-05-17 2002-11-21 Polimeri Europa S.P.A. Procede pour preparer des copolymeres et des terpolymeres elastomeres d'ep(d)m
US6861543B2 (en) 2001-05-17 2005-03-01 Polimeri Europa S.P.A. Process for the preparation of ep(d)m elastomeric copolymers and terpolymers
US7060765B2 (en) 2001-07-19 2006-06-13 Univation Technologies, Llc Low comonomer incorporating metallocene catalyst compounds
WO2003008465A3 (fr) * 2001-07-19 2003-08-28 Univation Tech Llc Composes catalyseurs a metallocene a faible incorporation de comonomere
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7339018B2 (en) 2002-12-05 2008-03-04 Exxonmobil Chemical Patents Inc. Diene-modified propylene copolymers
US7223828B2 (en) 2002-12-05 2007-05-29 Exxonmobil Chemical Patents Inc. Branched diene-modified crystalline polypropylene terpolymers
US7326756B2 (en) 2002-12-05 2008-02-05 Exxonmobil Chemical Patents Inc. High temperature bulk polymerization of branched crystalline polypropylene
WO2004052951A1 (fr) * 2002-12-05 2004-06-24 Exxonmobil Chemical Patents Inc. Copolymeres de propylene a modification dienique
EP1464657A1 (fr) * 2003-03-06 2004-10-06 ATOFINA Research Catalyseur du type métallocène hydrogené
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7994237B2 (en) 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
WO2012048067A3 (fr) * 2010-10-07 2012-11-22 Chevron Phillips Chemical Company Lp Systèmes de catalyseur métallocène ponté avec effets commutables de l'hydrogène et de comonomère

Also Published As

Publication number Publication date
RU2179561C2 (ru) 2002-02-20
DE69702569T2 (de) 2001-03-15
ES2148895T3 (es) 2000-10-16
KR970074808A (ko) 1997-12-10
CA2204177C (fr) 2006-06-20
JPH1067817A (ja) 1998-03-10
US6124413A (en) 2000-09-26
MX9703331A (es) 1998-04-30
DE69702569D1 (de) 2000-08-24
CN1172816A (zh) 1998-02-11
CA2204177A1 (fr) 1997-11-09
KR100257458B1 (ko) 2000-06-01
CN1098869C (zh) 2003-01-15
EP0806436B1 (fr) 2000-07-19
IT1283630B1 (it) 1998-04-23
ITMI960926A0 (fr) 1996-05-09
JP3986613B2 (ja) 2007-10-03
BR9703091A (pt) 1998-09-08
ITMI960926A1 (it) 1997-11-09

Similar Documents

Publication Publication Date Title
EP0806436B1 (fr) Procédé de préparation de copolymères EP(D)M élastomériques
EP0647243B1 (fr) Procede de preparation d'un copolymere ethylenique
MXPA97003331A (en) Processes to prepare copyright of styrene-propylene-dieno elastomeri
US6015868A (en) Substituted indenyl containing metal complexes and olefin polymerization process
EP1299405B1 (fr) Composes polycycliques a cycles accoles, complexes metalliques et procede de polymerisation
EP0923589B1 (fr) Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 3 et procede de polymerisation d'olefine
US6225427B1 (en) Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst
EP0955304B1 (fr) Metallocènes pontés pour la polymérisation d'oléfines
MXPA01004337A (es) Interpolimeros de alfa-olefina/etileno que disminuyen el esfuerzo cortante.
US5917072A (en) Catalysts for the polymerization of alpha-olefins
CA2646567A1 (fr) Complexes metalliques groupe 4 substitues, catalyseurs et procede de polymerisation olefinique
JP4275208B2 (ja) メタロセン、それらの製造およびアルファ−オレフィンの重合におけるそれらの使用
US20020165329A1 (en) Alkylphenyl-substituted group 4 metal complexes, catalysts and olefin polymerization process
US6806327B2 (en) Substituted polycyclic, fused ring compounds, metal complexes and polymerization process
US6872844B2 (en) Metal complexes containing acetylenic ligands, polymerization catalysts and addition polymerization process
US20020098973A1 (en) Bridged gallium or indium containing group 4 metal complexes
US6861543B2 (en) Process for the preparation of ep(d)m elastomeric copolymers and terpolymers
EP1497301B1 (fr) Complexes metalliques a noyau fusionne polycyclique substitue et leur procede de polymerisation
RU2172746C2 (ru) Катализаторы для полимеризации альфа-олефинов, способ гомо- и сополимеризации альфа-олефинов и способ получения эластомерных сополимеров этилена
MXPA96006464A (en) Catalysts for polymerization dealfa-olefi
HK1015791B (en) Metallocenes, their preparation and use in the polymerization of alphaolefins

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB NL

AX Request for extension of the european patent

Free format text: RO PAYMENT 970503

17P Request for examination filed

Effective date: 19980416

17Q First examination report despatched

Effective date: 19981223

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB NL

AX Request for extension of the european patent

Free format text: RO PAYMENT 19970503

REF Corresponds to:

Ref document number: 69702569

Country of ref document: DE

Date of ref document: 20000824

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2148895

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20160526

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160527

Year of fee payment: 20

Ref country code: ES

Payment date: 20160526

Year of fee payment: 20

Ref country code: GB

Payment date: 20160527

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160527

Year of fee payment: 20

Ref country code: FR

Payment date: 20160530

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69702569

Country of ref document: DE

Ref country code: NL

Ref legal event code: MK

Effective date: 20170502

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20170502

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20170502

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20170825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20170504